CN103980320A - Oil soluble molybdenum-based precursor of catalyst, preparation method and application thereof - Google Patents
Oil soluble molybdenum-based precursor of catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an oil soluble molybdenum-based precursor of a catalyst, a preparation method and application thereof, relating to the technical field of heavy oil hydrocracking catalysts and solving the problems of low catalytic hydrogenation activity and high cost of the existing catalysts. The preparation method for the precursor comprises the steps of (1) mixing a molybdenum source with water, reacting for 30-240 minutes at 70-90DEG C, and adding inorganic acid; (2) adding polycarbon alcohol into P2S5 in 5-15 minutes at 50-80DEG C, and reacting for 1-3 hours at 70-100DEG C; (3) adding the product of step (2) into the product of step (1), adding resin, and reacting for 4-8 hours at 70-110DEG C; (4) separating oil phase from the product of step (3) so as to obtain the target product. The precursor can form MoS2 active components through self sulfurization and in situ decomposition, is used in slurry reactor hydrocracking of poor heavy oil with high content of metal, carbon residue and sulfur, and can lower the yield of coke and keep a device to run for a long period.
Description
Technical field
The present invention relates to the technical field of heavy-oil hydrogenation cracking catalyst in refining of petroleum technique, refer to especially catalyst based presoma of a kind of oil-soluble molybdenum and its preparation method and application.
Background technology
The cracking of heavy oil slurry state bed hydroprocessing is the heavy-oil hydrogenation thermocracking process under high hydrogen pressure, high temperature.A small amount of catalyst precursor fully contacts with hydrogen with raw material residual oil in reactor, be full back-mixing state, organic-molybdenum catalyst precursor is dissolved in stock oil, the Main Function of catalyst precursor is that self-vulcanizing generates the moly-sulfide with hydrogenation activity in residual oil, thereby bury in oblivion the free radical of residual oil in thermal cracking processes, suppress condensation, reduce green coke, there is lower green coke amount and reach again higher transformation efficiency thereby realize whole hydrogenation process.Petroleum refining industry both domestic and external is faced with severeer situation: petroleum resources deficiency, crude quality variation, cut become heavy trend and increasingly sharpen; Meanwhile, petroleum products demand structure is also being changed, petroleum chemicals face the requirement of upgrading.Heavy oil is as the very important energy of one, and successfully these resources of development and utilization are very crucial for the future of petrochemical industry.Along with the increase to intermediate oil demand, heavy feed stock deep processing changes into high-quality light-end products and becomes more and more meaningful, and hydrocracking process has higher light-end products productive rate, so just more and more more paid close attention to.
The scarcity day by day of the continuous increase of petroleum products demand and high-quality crude resource, in the urgent need to effective processing means of exploitation inferior feedstock oil.Wherein, residual hydrogenation is a kind of important processing means, and at present, the Residue Hydrotreating Technology of exploitation has fixed bed, ebullated bed, slurry bubble bed technique.The research of slurry bubble bed hydrogen addition technology is more active from the eighties in 20th century, tens kinds of EST technology and the Novel slurry bed hydroprocessing technology of domestic petroleum university (East China) exploitation etc. of the at present VOP-Aurabon technique that has German VCC technology, Canadian CANMET technique, UOP of report, the exploitation of Italian ENI company, but at present,, these technology are mostly in Industrial demonstration or pilot scale stage; Slurry bubble bed hydrogenation technique can be processed the inferior heavy oil of high metal (mass content of nickel and vanadium is more than 100 μ g/g), high carbon residue (mass content of carbon residue is greater than 15%), high-sulfur (mass content of sulphur is greater than 2.0%), and light oil yield is high, especially diesel oil distillate yield is high, good product quality, the character of the good product quality of the handiness of decarburization technique and hydrogenation technique is combined, overcome some problems that existing industrialization technology exists.The catalyzer that is applied to this technique is mainly dispersed catalyzer, these catalyzer generate very little metallic sulfide by catalyst precursor in sulfur in heavy oilization, because these small-particle dispersity are high, the ability of the macromolecular radical generating in activation hydrogen and saturated residual oil thermo-cracking is strong, so, hydrogenation and press down burnt better performances, therefore develop the catalyst precursor of the novel energy self-vulcanizing with high oil dissolubility, the popularization of residual oil slurry bubble bed hydrogenation technique is had great significance.
But according to relevant research, the current catalyst based presoma of residual oil slurry bubble bed hydrocracking oil-soluble molybdenum need add vulcanizing agent and just can convert the moly-sulfide (Mo with catalytic activity to
xs
y, x and y are natural number) and actives, this process increases running cost, and increases the resistance to mass transfer in sulfuration, causes sulfuration difficulty large, and the moly-sulfide particle diameter of growth is large, has reduced catalytic hydrogenation activity, and then aggravates the coking reaction in hydrocracking process.Therefore, synthetic a kind of sulfur-bearing organic-molybdenum presoma can not add vulcanizing agent and just can be combined with the sulphur of self and generate metallic sulfide in sulfidation, has reduced resistance to mass transfer, and the metallic sulfide that promotes sulfuration generation to have greater activity is very important.
Summary of the invention
The present invention proposes catalyst based presoma of a kind of oil-soluble molybdenum and its preparation method and application, has solved catalyst with base of molybdenum presoma in prior art and need to add vulcanizing agent and just can convert the moly-sulfide actives with catalytic activity to and cause the low and production cost high problem of catalytic hydrogenation activity.
The catalyst based presoma of a kind of oil-soluble molybdenum that the present invention proposes, its technical scheme is achieved in that to have following formula:
In formula, R
1～R
8be selected from C
3～C
16alkyl or aromatic base group.
The catalyst based presoma of oil-soluble molybdenum of the present invention is a kind of phosphorous self-vulcanizing catalyst with base of molybdenum presoma, and it at room temperature has good mobility, and condensation point is lower, is easy to store and transport; Meanwhile, this presoma oil soluble is good, is easy to residual oil and dissolves each other, and in reaction process, generates approximate nano level catalytic activity thing, and its catalytic hydrogenation activity is high; In addition, the phosphorus in this presoma is produced phosphide in reaction process, and the phosphide that reaction generates has good hydrogenation desulfurization and denitrogenation performance.
The preparation method of the catalyst based presoma of a kind of oil-soluble molybdenum that the present invention proposes, its technical scheme is achieved in that and comprises the following steps:
1) by molybdenum source and water with the mixed in molar ratio of 1:10～2:1, at 70～90 DEG C, react 30～240min, be cooled to 30～50 DEG C, add mineral acid, make solution be neutral;
2) be 3:1～5:1 according to the mol ratio of hydroxyl in higher alcohols and thiophosphoric anhydride, higher alcohols is joined in thiophosphoric anhydride, adding temperature is 50～80 DEG C, interpolation time 5～15min, after interpolation, be at 70～100 DEG C in temperature, reaction 1～3h, the hydrogen sulfide generating in inert gas purge reaction;
3) by step 2) products therefrom joins step 1) in products therefrom, and add acidic cation-exchange resin, the quality of acidic cation-exchange resin be in molybdenum source molybdenum quality 10～15%, at 70～110 DEG C, reaction 4～8h;
4) by step 3) products therefrom separates, and removes lower floor's water and resin, gets oil phase, and washing oil phase, obtains the catalyst based presoma of oil-soluble molybdenum.
The preparation method of the catalyst based presoma of oil-soluble molybdenum of the present invention reacts with thiophosphoric anhydride by higher alcohols and forms phosphorous organosulfur compound; React with water by molybdenum source, under the effect of mineral acid, generate molybdenum source compound; Phosphorous organosulfur compound is reacted with molybdenum source compound again, thereby make this catalyst precursor.This preparation method's technical process is short, and temperature of reaction is low, and the reaction times is short, is convenient to control, and easy to operate, energy consumption is low; Product layering is fast, easily separated, and raw material is easy to get, and low price greatly reduces production cost, is easy to realize industrialization.
Further, the mol ratio of the molybdenum in described thiophosphoric anhydride, molybdenum source, mineral acid is 2:1:1.5～5.5:1:0.5.Fully regulate mole proportioning of sulphur in reaction raw materials, phosphorus, molybdenum and acid, carry out thereby react fully, avoid wastage of material.
Further, described step 4) in, washing times is 2～3 times, after washing, by centrifugation or underpressure distillation, to remove unnecessary moisture.By repeatedly washing, improve the purity of this catalyst precursor, by centrifugation or underpressure distillation, the water in oil phase is fully removed, separate simply convenient operation.
Described higher alcohols is C
3～C
16alkyl alcohol or aromatic alcohol.These higher alcoholses are conventional higher alcohols, and raw material is easy to get, and low price can reduce production costs greatly.
Further, described higher alcohols is C
3～C
16branched secondary alcohol.Contain in same carbon atoms number object alkyl, the abrasion resistance of secondary carbon back is better than primary carbon base, and the anti-wear of branched alkane can be better than straight-chain paraffin.Therefore, select branched many carbon secondary alcohol can improve the wear resisting property of catalyst precursor.
Described molybdenum source compound is the one in molybdic oxide, Sodium orthomolybdate or ammonium molybdate.
Described acidic cation-exchange resin is that sodium type Zeo-karb is Hydrogen acidic cation-exchange resin through vitriolization.The use of Hydrogen acidic cation-exchange resin, can simplify synthesis step, has improved the yield of target product, has reduced production cost.
The application of the catalyst based presoma of a kind of oil-soluble molybdenum that the present invention proposes, its technical scheme is achieved in that the inferior heavy slurry oil state bed hydroprocessing cracking technique of the catalyst based presoma of described oil-soluble molybdenum for containing high metal, high carbon residue, high-sulfur.
The catalyst based presoma of oil-soluble molybdenum of the present invention can be starched state bed hydroprocessing cracking technique for inferior heavy oil, particularly contain the inferior heavy slurry oil state bed hydroprocessing cracking technique of high metal, high carbon residue and high-sulfur, metal content high (mass content of nickel and vanadium is more than 100 μ g/g) in this inferior heavy oil, also high (mass content of sulphur is greater than 2.0%) of carbon residue content high (mass content of carbon residue is greater than 15%), sulphur content; This phosphorous self-vulcanizing catalyst with base of molybdenum presoma oil soluble can be good, in this inferior heavy oil, easily disperses, and sulfur product particle diameter can reach nano level, and catalytic activity is high; In catalytic hydrocracking reaction, generate phosphide, this phosphide has good hydrogenation desulfurization and denitrogenation performance.
Further, described oil-soluble catalyst presoma directly adds in the inferior heavy oil that contains high metal, high carbon residue, high-sulfur, and the molybdenum in described oil-soluble catalyst presoma is 50～2000 μ g/g in the ratio of heavy oil feedstock.This oil-soluble catalyst presoma usage quantity is few, and catalytic activity is high, and metal recovery rate is higher, can be up to 90.23%.
Beneficial effect of the present invention:
(1) the phosphorous self-vulcanizing catalyst with base of molybdenum of the oil soluble presoma that the present invention proposes is the molybdenum base organic compound that a kind of oil soluble can be excellent, there is no at present this material and be applied to the cracking reaction of inferior heavy slurry oil state bed hydroprocessing, use the phosphorous self-vulcanizing catalyst with base of molybdenum of oil soluble of the present invention presoma to be applied in the cracking of inferior heavy slurry oil state bed hydroprocessing and can change into the nano-scale particle Mo with catalytic hydrogenation activity by bin cure
xs
y(x, y is natural number), can reduce coke yield, holdout device long-term operation; Because when coke yield is high, easily occluding device, shortens the cycle of operation of device.
(2) the phosphorous self-vulcanizing catalyst with base of molybdenum of oil soluble provided by the invention presoma has good dispersiveness, can be dissolved in preferably in residual oil, in dispersing technology process, do not need to add any vulcanizing agent and can original position generate the molybdenumdisulphide with catalytic activity, on the one hand, avoid the use of catalyst precursor and vulcanizing agent mixing equipment, thereby reduced production cost; On the other hand, sulfur-bearing in molybdenum base organic compound self molecule, when sulfuration molybdenum with around element sulphur be combined and generate moly-sulfide active ingredient, thereby reduced resistance to mass transfer and then accelerated vulcanization rate minimizing curing time; In addition, exactly because the oily organic-molybdenum that this product is thickness can be dissolved in oil phase, bin cure changes into short grained moly-sulfide, and be difficult for coagulation and deposition occur, and can ensure that in catalyst precursor, metallic element is all converted into metal sulphide, ensured higher catalytic activity.These have greatly improved catalytic activity and have also simplified dispersion and sulfidation that heavy oil is starched catalyzer in state bed hydroprocessing technology.The economic benefit of whole heavy oil upgrading technique is enhanced.
(3) the phosphorous self-vulcanizing catalyst with base of molybdenum of oil soluble provided by the invention precursor synthesis technique is simple, mild condition, and the raw materials such as alcohols are easy to get, low price, thus greatly reduce production cost.
(4) the present invention uses acidic cation ion exchange resin, simplifies synthesis step, has improved the yield of target product, has reduced production cost.
(5) the moly-sulfide active ingredient that self-vulcanizing of the present invention is produced, particle diameter is less, and energy high dispersing is in heavy oil, there is higher hydrogenation activity, can suppress preferably the generation of coke, add can reach on a small quantity and press down preferably burnt effect, save production cost and operating procedure is simple.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the infrared spectrogram of the embodiment of the present invention one products therefrom;
Fig. 2 is the infrared spectrogram of the embodiment of the present invention two products therefroms;
Fig. 3 is the infrared spectrogram of the embodiment of the present invention three products therefroms;
Fig. 4 is the infrared spectrogram of the embodiment of the present invention four products therefroms.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The catalyst based presoma of a kind of oil-soluble molybdenum, has following formula:
In formula, R
1～R
8be selected from C
3～C
16alkyl or aromatic base group.
A preparation method for the catalyst based presoma of oil-soluble molybdenum, comprises the following steps:
1) by molybdenum source and water with the mixed in molar ratio of 1:10～2:1, at 70～90 DEG C, react 30～240min, be cooled to 30～50 DEG C, drip mineral acid, make solution be neutral;
2) be 3:1～5:1 according to the mol ratio of hydroxyl in higher alcohols and thiophosphoric anhydride, higher alcohols is joined in thiophosphoric anhydride, adding temperature is 50～80 DEG C, interpolation time 5～15min, after interpolation, be at 70～100 DEG C in temperature, reaction 1～3h, the hydrogen sulfide generating in inert gas purge reaction;
3) by step 2) products therefrom joins step 1) in products therefrom, and add acidic cation-exchange resin, the quality of acidic cation-exchange resin be in molybdenum source molybdenum quality 10～15%, at 70～110 DEG C, reaction 4～8h;
4) by step 3) products therefrom separates, and removes lower floor's water and resin, gets oil phase, and washing oil phase, obtains the catalyst based presoma of oil-soluble molybdenum.
Further, the mol ratio of the molybdenum in described thiophosphoric anhydride, molybdenum source, mineral acid is 2:1:1.5～5.5:1:0.5.
Further, described step 4) in, washing times is 2～3 times, after washing, by centrifugation or underpressure distillation, to remove unnecessary moisture.
Described higher alcohols is C
3～C
16alkyl alcohol or aromatic alcohol.Further, described higher alcohols is C
3～C
16branched secondary alcohol.
Described molybdenum source compound is the one in molybdic oxide, Sodium orthomolybdate or ammonium molybdate.
Described acidic cation-exchange resin is that sodium type Zeo-karb is Hydrogen acidic cation-exchange resin through vitriolization.
An application for the catalyst based presoma of oil-soluble molybdenum, the inferior heavy slurry oil state bed hydroprocessing cracking technique of the catalyst based presoma of described oil-soluble molybdenum for containing high metal, high carbon residue, high-sulfur.
Further, described oil-soluble catalyst presoma directly adds in the inferior heavy oil that contains high metal, high carbon residue, high-sulfur, and the molybdenum in described oil-soluble catalyst presoma is 50～2000 μ g/g in the ratio of heavy oil feedstock.
Embodiment mono-
Get 0.5mol MoO
3with 1.2mol NaOH, add 5mol water, in the water-bath of 70 DEG C, stirring and refluxing 240min, is cooled to 40 DEG C, adds the dense H of 0.75mol
2sO
4, make solution be neutral, obtain molybdenum source compound; Get the propyl carbinol of 3.0mol and the mixing solutions of isooctyl alcohol adds in dropping funnel, dropwise add the P that 1.0mol is housed
2s
5in round-bottomed flask, dropping temperature is 80 DEG C, time for adding 5min, and after dropwising, in 80 DEG C of reaction 3h, magnetic agitation solution pass into nitrogen in reaction process, constantly purges, to remove the hydrogen sulfide of generation; Filter elimination unreacted P completely
2s
5, filtrate is moved in dropping funnel, and be added dropwise in above-mentioned molybdenum source compound, in mixing solutions, add 4.8g acidic cation ion exchange resin, stirring and refluxing reaction 4h at 95 DEG C; Filter, leave standstill, separate, remove lower floor's water and resin, get oil phase, washing oil phase, obtains brown color oily liquids, product yield 87%, and code name is C-1.
By product C-1 described in aforesaid method, the Nexus type Fourier transformation infrared spectrometer generating in Thermo Nicolet company carries out examination of infrared spectrum, and Fig. 1 has listed the infrared spectrogram of the phosphorous self-vulcanizing catalyst precursor of this oil soluble; As seen from Figure 1,2966cm
-1for-CH
3asymmetrical stretching vibration peak, 2868cm
-1for-CH
3symmetry and asymmetrical stretching vibration peak; 2850cm
-1for-CH
2-asymmetrical stretching vibration peak; 1384cm
-1, 1461cm
-1for-CH
3flexural vibration peak; 1018cm
-1for P-O-C absorbs vibration peak; 981cm
-1for Mo=O eigen vibration peak; 660cm
-1for the stretching vibration peak of P=S; 476.3cm
-1for the charateristic avsorption band of molybdenum sulphur ring.Comprehensive above known, this synthetic oily brown color organic compound is target product.
Embodiment bis-
Get 0.5mol Na
2moO
42H
2o, adds 0.25mol water, and in the water-bath of 80 DEG C, stirring and refluxing 30min, is cooled to 30 DEG C, splashes into the dense H of 0.5mol
2sO
4, acidifying, obtains molybdenum source compound; Get 4.5mol isooctyl alcohol and add in dropping funnel, dropwise splash into the P that 1.5mol is housed
2s
5in round-bottomed flask, dropping temperature is 50 DEG C, and time for adding 10min, after dropwising, is at 90 DEG C in temperature, and reaction 2h, in reaction process, adopts magnetic agitation, and passes into nitrogen and constantly purge, to remove the hydrogen sulfide of generation; Cooling, filter elimination unreacted P completely
2s
5filtrate is moved in dropping funnel, and be added dropwise in above-mentioned molybdenum source compound, and add 6g acidic cation-exchange resin, described acidic cation-exchange resin is that sodium type Zeo-karb is Hydrogen acidic cation-exchange resin through vitriolization, at 70 DEG C, stirring and refluxing reaction 8h; Be cooled to after room temperature, remove by filter acidic cation-exchange resin, by after filtrate stratification, get oil phase, wash 2 times, moisture is removed in underpressure distillation, obtains brown color oily liquids, product yield 88%, and code name is C-2.
By product C-2 described in aforesaid method, the Nexus type Fourier transformation infrared spectrometer generating in Thermo Nicolet company carries out examination of infrared spectrum, and Fig. 2 has listed the infrared spectrogram of the phosphorous self-vulcanizing catalyst precursor of this oil soluble; As seen from Figure 2,2966cm
-1for-CH
3asymmetrical stretching vibration peak, 2868cm
-1for-CH
3symmetry and asymmetrical stretching vibration peak; 2850cm
-1for-CH
2-asymmetrical stretching vibration peak; 1384cm
-1, 1461cm
-1for-CH
3flexural vibration peak; 1018cm
-1for P-O-C absorbs vibration peak; 981cm
-1for Mo=O eigen vibration peak; 660cm
-1for the stretching vibration peak of P=S; 476.3cm
-1for the charateristic avsorption band of molybdenum sulphur ring.Comprehensive above known, this synthetic oily brown color organic compound is target product.
Embodiment tri-
Get 0.5mol MoO
3, add 0.5mol water, in the water-bath of 90 DEG C, stirring and refluxing 180min, is cooled to 50 DEG C, splashes into 0.5mol mineral acid, makes solution be neutral, obtains molybdenum source compound; The mixing solutions (phenylcarbinol: isooctyl alcohol=1:1) of getting 5.0mol phenylcarbinol and isooctyl alcohol adds in dropping funnel, dropwise splashes into the P that 1.0mol is housed
2s
5in round-bottomed flask, dropping temperature is 50 DEG C, time for adding 15min, and after dropwising, at 90 DEG C, reaction 2h, in reaction process, magnetic agitation also passes into argon gas and constantly purges, and removes the hydrogen sulfide of generation; Filter elimination unreacted P completely
2s
5, filtrate is moved in dropping funnel, be added dropwise to above-mentioned molybdenum source compound, and add 7.2g acidic cation-exchange resin, at 95 DEG C, stirring and refluxing reaction 4h; Filter, leave standstill, separate, washing, obtains red-brown oily liquids, product yield 85%, and code name is C-3.
By product C-3 described in aforesaid method, the Nexus type Fourier transformation infrared spectrometer generating in Thermo Nicolet company carries out examination of infrared spectrum, and Fig. 3 has listed the infrared spectrogram of the phosphorous self-vulcanizing catalyst precursor of this oil soluble; As seen from Figure 3,2966cm
-1for-CH
3asymmetrical stretching vibration peak, 2868cm
-1for-CH
3symmetry and asymmetrical stretching vibration peak; 2850cm
-1for-CH
2-asymmetrical stretching vibration peak; 1384cm
-1, 1461cm
-1for-CH
3flexural vibration peak; 1018cm
-1for P-O-C absorbs vibration peak; 981cm
-1for Mo=O eigen vibration peak; 660cm
-1for the stretching vibration peak of P=S; 476.3cm
-1for the charateristic avsorption band of molybdenum sulphur ring.Comprehensive above known, this synthetic oily red-brown organic compound is target product.
Embodiment tetra-
Get 0.5mol Na
2moO
42H
2o, adds 2.5mol water, and in the water-bath of 90 DEG C, stirring and refluxing 30min, is cooled to 30 DEG C, drips the dense H of 0.5mol
2sO
4, acidifying, obtains molybdenum source compound; The mixing solutions (hexadecanol: phenylcarbinol=1:1) of getting 8.0mol hexadecanol and phenylcarbinol adds in dropping funnel, dropwise splashes into the P that is added with 2.0mol
2s
5in round-bottomed flask, dropping temperature is 50 DEG C, and time for adding 10min, after dropwising, at 80 DEG C, reacts 1h in oil bath, and in reaction process, magnetic agitation also passes into helium and constantly purges, and removes the hydrogen sulfide of generation; Cooling, suction filtration, elimination unreacted P completely
2s
5, filtrate is moved in dropping funnel, splashed in above-mentioned molybdenum source compound, and added 4.8g acidic cation-exchange resin, at 95 DEG C, stirring and refluxing reaction 4h; Cool to room temperature, filters, and leaves standstill, and separates, and washes 3 times, and centrifugation is removed after moisture, obtains red-brown oily liquids, product yield 84%, and code name is C-4.
By product C-4 described in aforesaid method, the Nexus type Fourier transformation infrared spectrometer generating in Thermo Nicolet company carries out examination of infrared spectrum, and Fig. 4 has listed the infrared spectrogram of the phosphorous self-vulcanizing catalyst precursor of this oil soluble; As seen from Figure 4,2966cm
-1for-CH
3asymmetrical stretching vibration peak, 2868cm
-1for-CH
3symmetry and asymmetrical stretching vibration peak; 2850cm
-1for-CH
2-asymmetrical stretching vibration peak; 1384cm
-1, 1461cm
-1for-CH
3flexural vibration peak; 1018cm
-1for P-O-C absorbs vibration peak; 981cm
-1for Mo=O eigen vibration peak; 660cm
-1for the stretching vibration peak of P=S; 476.3cm
-1for the charateristic avsorption band of molybdenum sulphur ring.Comprehensive above known, this synthetic oily red-brown organic compound is target product.
Embodiment five
Get 0.5mol ammonium molybdate and add in 5mol water, in the water-bath of 90 DEG C, stirring and refluxing 60min, is cooled to 50 DEG C; Splash into 0.25mol mineral acid, make solution be neutral, obtain molybdenum source compound; The isooctyl alcohol of getting 5mol adds in dropping funnel, at the temperature of 60 DEG C, in 10min, dropwise splashes into the P that 1mol is housed
2s
5in round-bottomed flask, magnetic agitation also passes into nitrogen, constantly purges the hydrogen sulfide of removing generation, 70 DEG C of reaction 2h; Filter, elimination unreacted thiophosphoric anhydride completely, filtrate is moved in dropping funnel, and joined in above-mentioned molybdenum source compound, in solution, add 6g acidic cation-exchange resin, described acidic cation-exchange resin is that sodium type Zeo-karb is Hydrogen acidic cation-exchange resin through vitriolization, 70 DEG C of stirring and refluxing reaction 4h; Products therefrom separates, and removes lower floor's water and resin, gets oil phase, and washing oil phase, obtains brown color oily liquids, and product yield is 84%, known through Infrared spectroscopy, and this brown color oily liquids is the catalyst based presoma of oil-soluble molybdenum.
Embodiment six
Get 0.5mol MoO
3with 1.2mol NaOH, add 5mol water, mix, at 80 DEG C, reaction 120min, is cooled to 30 DEG C, splashes into the rare H of 0.25mol
2sO
4, acidifying, obtains molybdenum source compound; Get the Virahol of 11.0mol, add in dropping funnel, and it is progressively added drop-wise in the thiophosphoric anhydride of 2.75mol, dropping temperature is 50 DEG C, and time for adding 15min, after dropwising, be at 100 DEG C in temperature, reaction 1h, in reaction process, the hydrogen sulfide that adopts inert gas purge reaction to generate; Reacted product is joined in above-mentioned molybdenum source compound, and add 4.8g acidic cation-exchange resin, described acidic cation-exchange resin is that sodium type Zeo-karb is Hydrogen acidic cation-exchange resin through vitriolization, at 110 DEG C, and reaction 6h; After having reacted, product is separated, remove lower floor's water and resin, get oil phase, washing oil phase, obtains brown color oily liquids, product yield 85%, and known through Infrared spectroscopy, this brown color oily liquids is the catalyst based presoma of oil-soluble molybdenum.
Embodiment seven
Get 0.5mol Sodium orthomolybdate, add 1.0mol water, in the water-bath of 90 DEG C, stirring and refluxing 30min, is cooled to 50 DEG C, splashes into 0.75mol nitric acid, makes solution be neutral, obtains molybdenum source compound; The isooctyl alcohol of getting 11.0mol adds in dropping funnel, dropwise splashes into the P that 2.75mol is housed
2s
5in round-bottomed flask, when dropping, control temperature 60 C, control 10min and dropwise, after dropwising, in 70 DEG C of reaction 2h, in reaction process, magnetic agitation also passes into rare gas element, constantly purges, to remove the hydrogen sulfide of generation; Product is added in above-mentioned molybdenum source compound, and add 7.2g acidic cation-exchange resin, at 70 DEG C, stirring and refluxing reaction 4h; Filter, leave standstill, separate, obtain oil phase, washing oil phase is to neutral, and centrifugation, removes moisture, obtains brown color oily liquids, and product yield 88% is known through Infrared spectroscopy, and this brown color oily liquids is the catalyst based presoma of oil-soluble molybdenum.
The catalyst based presoma of oil-soluble molybdenum of the present invention can be for the inferior heavy slurry oil state bed hydroprocessing cracking technique that contains high metal, high carbon residue, high-sulfur, its using method is, catalyst based this oil-soluble molybdenum presoma is directly added in the inferior heavy oil that contains high metal, high carbon residue, high-sulfur, in use procedure, in the catalyst based presoma of described oil-soluble molybdenum, molybdenum is 50～2000 μ g/g in the ratio of heavy oil feedstock.
The long residuum of getting four kinds of catalyst with base of molybdenum presomas (C-1, C-2, C-3 and C-4) in embodiment mono-, embodiment bis-, embodiment tri-and embodiment tetra-and the super viscous crude of Kelamayi Feng Cheng mixes (its character is in table 1), in autoclave, be under 7MPa in 430 DEG C, hydrogen first pressing, reaction 60min, table 2 has listed that to carry out in gained catalyst with base of molybdenum presoma of the present invention and prior art molybdenum naphthenate be feedstock conversion situation after the reaction conditions of catalyst precursor (adding sulphur powder) in this catalytic hydrocracking reaction process and reaction.As shown in Table 2, compared with molybdenum naphthenate, the in the situation that of same catalyst presoma addition, the phosphorous self-vulcanizing catalyst with base of molybdenum of oil soluble provided by the invention presoma gained coking yield, all lower than 1.00%, has advantages of that catalytic activity is high, it is good to press down burnt performance; This catalyst with base of molybdenum presoma is applied in residual oil, can control coke yield <1.0%, and 500 DEG C of liquid product yields of < reach 60～70%; The increase of this catalyst with base of molybdenum addition in residual oil, can effectively control the generation of coke, in the time that the addition of molybdenum in residual oil reaches 2000 μ g/g, almost can't detect the generation of coke in product.
The catalyst based precursor synthesis technique of oil-soluble molybdenum of the present invention is simple, and mild condition is convenient to realize; Raw material is cheaply easy to get, and greatly reduces production cost; Can starch state bed hydroprocessing cracking technique for inferior heavy oil, particularly contain the inferior heavy slurry oil state bed hydroprocessing cracking technique of high metal (mass content of nickel and vanadium is more than 100 μ g/g), high carbon residue (mass content of carbon residue is greater than 15%) and high-sulfur (mass content of sulphur is greater than 2.0%); This phosphorous self-vulcanizing catalyst with base of molybdenum presoma oil soluble can be good, in this inferior heavy oil, easily disperses, and sulfur product particle diameter can reach nano level, and catalytic activity is high; In catalytic hydrocracking reaction, generate phosphide, this phosphide has good hydrogenation desulfurization and denitrogenation performance.
The long residuum character of the super viscous crude of table 1 Kelamayi Feng Cheng
Table 2 autoclave evaluation result
Remarks: the calculation formula of each product yield is:
The quality of m---material, the g of unit.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the catalyst based presoma of oil-soluble molybdenum, is characterized in that, has following formula:
In formula, R
1～R
8be selected from C
3～C
16alkyl or aromatic base group.
2. a preparation method for the catalyst based presoma of oil-soluble molybdenum according to claim 1, is characterized in that, comprises the following steps:
1) by molybdenum source and water with the mixed in molar ratio of 1:10～2:1, at 70～90 DEG C, react 30～240min, be cooled to 30～50 DEG C, add and add mineral acid, make solution be neutral;
2) be 3:1～5:1 according to the mol ratio of hydroxyl in higher alcohols and thiophosphoric anhydride, higher alcohols is joined in thiophosphoric anhydride, adding temperature is 50～80 DEG C, interpolation time 5～15min, after higher alcohols adds, be at 70～100 DEG C in temperature, reaction 1～3h, the hydrogen sulfide generating in inert gas purge reaction;
3) by step 2) products therefrom joins step 1) in products therefrom, and add acidic cation-exchange resin, the quality of acidic cation-exchange resin be in molybdenum source molybdenum quality 10～15%, at 70～110 DEG C, reaction 4～8h;
4) by step 3) products therefrom separates, and removes lower floor's water and resin, gets oil phase, and washing oil phase, obtains the catalyst based presoma of oil-soluble molybdenum.
3. the preparation method of the catalyst based presoma of oil-soluble molybdenum according to claim 2, is characterized in that: the molybdenum in described thiophosphoric anhydride, molybdenum source, the mol ratio of mineral acid are 2:1:1.5～5.5:1:0.5.
4. the preparation method of the catalyst based presoma of oil-soluble molybdenum according to claim 3, is characterized in that: described step 4) in, washing times is 2～3 times, after washing, by centrifugation or underpressure distillation, to remove unnecessary moisture.
5. the preparation method of the catalyst based presoma of oil-soluble molybdenum according to claim 2, is characterized in that: described higher alcohols is C
3～C
16alkyl alcohol or aromatic alcohol.
6. the preparation method of the catalyst based presoma of oil-soluble molybdenum according to claim 4, is characterized in that: described higher alcohols is C
3～C
16branched secondary alcohol.
7. the preparation method of the catalyst based presoma of oil-soluble molybdenum according to claim 2, is characterized in that: described molybdenum source compound is the one in molybdic oxide, Sodium orthomolybdate or ammonium molybdate.
8. the preparation method of the catalyst based presoma of oil-soluble molybdenum according to claim 2, is characterized in that: described acidic cation-exchange resin is that sodium type Zeo-karb is Hydrogen acidic cation-exchange resin through vitriolization.
9. an application for the catalyst based presoma of oil-soluble molybdenum according to claim 1, is characterized in that: the inferior heavy slurry oil state bed hydroprocessing cracking technique of the catalyst based presoma of described oil-soluble molybdenum for containing high metal, high carbon residue, high-sulfur.
10. the application of the catalyst based presoma of oil-soluble molybdenum according to claim 9, it is characterized in that: described oil-soluble catalyst presoma directly adds in the inferior heavy oil that contains high metal, high carbon residue, high-sulfur, the molybdenum in described oil-soluble catalyst presoma is 50～2000 μ g/g in the ratio of heavy oil feedstock.
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